JPH08253877A - Composite coating having abrasion resistance - Google Patents

Composite coating having abrasion resistance

Info

Publication number
JPH08253877A
JPH08253877A JP7333729A JP33372995A JPH08253877A JP H08253877 A JPH08253877 A JP H08253877A JP 7333729 A JP7333729 A JP 7333729A JP 33372995 A JP33372995 A JP 33372995A JP H08253877 A JPH08253877 A JP H08253877A
Authority
JP
Japan
Prior art keywords
particles
lubricant
coating
hard material
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP7333729A
Other languages
Japanese (ja)
Inventor
John Antony Peters
アントニー ピーターズ ジョン
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sulzer Markets and Technology AG
Original Assignee
Sulzer Innotec AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Sulzer Innotec AG filed Critical Sulzer Innotec AG
Publication of JPH08253877A publication Critical patent/JPH08253877A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/02—Parts of sliding-contact bearings
    • F16C33/04—Brasses; Bushes; Linings
    • F16C33/043—Sliding surface consisting mainly of ceramics, cermets or hard carbon, e.g. diamond like carbon [DLC]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F7/00—Casings, e.g. crankcases or frames
    • F02F2007/0097—Casings, e.g. crankcases or frames for large diesel engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C2206/00—Materials with ceramics, cermets, hard carbon or similar non-metallic hard materials as main constituents
    • F16C2206/80—Cermets, i.e. composites of ceramics and metal
    • F16C2206/82—Cermets, i.e. composites of ceramics and metal based on tungsten carbide [WC]

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

PROBLEM TO BE SOLVED: To prepare a composite coating by reducing wear in a ring and a cylinder bush as much as possible, preventing the occurrence of coagulation wear when lubrication is not enough, preventing cracks caused by fatigue and storing a suitable solid lubricant which is prepared for the lack of lubrication, in a layer.
SOLUTION: A composite coating 1 having resistance to wear and which contains a mixture of particles 3 of a hard material and particles 5 of a solid lubricant 6 is applied onto a substrate 2. The particles 3, 5 are incorporated in a binder alloy 4. The respective particles of the lubricant 6 are enclosed by a protective envelope 7. The protective envelope 7 prevents the bonding of the components of the lubricant 6 to the components of the binder alloy 4 and the particles 3 of the hard material.
COPYRIGHT: (C)1996,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、基板上に配置され
るとともに、硬質材料の粒子及び固形の潤滑剤の粒子の
混合物を有する耐摩滅性のある複合コーティングに関す
るものである。FIELD OF THE INVENTION The present invention relates to an abrasion resistant composite coating disposed on a substrate and having a mixture of particles of hard material and particles of solid lubricant.

【０００２】[0002]

【従来の技術】複合コーティングは欧州特許出願公開第
０２６５８００号において周知である。この複合コーテ
ィングにおいては、硬質材料の粒子、即ち炭化クロム又
はホウ化クロムの粒子が銅又は銅合金のマトリックスに
埋入するように組み込まれている。マトリックスの比率
は５〜１５重量％に達することが好ましい。例えば、コ
ーティングは粉末を溶かした液体を溶射することにより
なされ、粉末粒子は硬質材料相及びマトリックス材料の
双方を有する。この均質な噴霧用粉末に粉末状の更なる
材料を混合することが可能である。この材料は保護層に
自己潤滑特性を付与する。この種の材料の例としてコバ
ルト−ニッケル合金が提案されている。Composite coatings are well known from EP 0265800. In this composite coating, particles of hard material, i.e. chromium carbide or chromium boride, are embedded in a copper or copper alloy matrix. The proportion of matrix preferably amounts to 5-15% by weight. For example, the coating is made by spraying a liquid in which the powder is melted, the powder particles having both a hard material phase and a matrix material. It is possible to mix further materials in powder form with this homogeneous atomizing powder. This material imparts self-lubricating properties to the protective layer. Cobalt-nickel alloys have been proposed as an example of this type of material.

【０００３】例えば、この周知の複合層は大容量のディ
ーゼル機関におけるピストンリングの回転層として使用
可能である。ピストンリングがシリンダスリーブとの相
互作用により動的な密封作用を行うように、ピストンリ
ングの回転層の最適材料が選択される。このためには次
の要素が考慮されるべきである。ａ）リング及びシリン
ダブッシュにおける摩耗を極力低減する。ｂ）潤滑が不
十分である場合、できる限り凝着摩耗が生じないように
する。即ち、「すり減り危険性」を低減し、つまり層を
「耐すり減り性」にする（「耐すり減り性」は独語の
「耐燃焼痕性（Brandspursicherheit）」に相当す
る）。ｃ）更に、疲労に起因する亀裂が生じないように
する。ｄ）最後に潤滑が不足する場合に備え、適正な固
形潤滑剤を層の中に貯えておく。For example, this known composite layer can be used as a rotating layer for piston rings in high capacity diesel engines. The optimum material for the rotating layer of the piston ring is selected so that the piston ring provides a dynamic sealing action by interaction with the cylinder sleeve. The following factors should be considered for this: a) Minimize wear on rings and cylinder bushes. b) If there is insufficient lubrication, avoid cohesive wear as much as possible. That is, it reduces the "scuffing risk", i.e. makes the layer "scratch resistant"("scratchresistant" corresponds to the German word "Brandspursicherheit"). c) Furthermore, prevent cracks due to fatigue from occurring. d) Finally, in case of lack of lubrication, store the proper solid lubricant in the layer.

【０００４】炭化タングステン（WC）が硬質材料として
機能し、硬質材料の粒子がコバルト−クロム合金のマト
リックスにより固着された耐性の高い複合層が周知であ
る。このマトリックス、即ち結合剤合金は潤滑効果を有
するが、潤滑が不足する場合にはその効果は不十分であ
る。従って、固形潤滑剤を混合することが必要である。
１つの試みとして、潤滑剤として黒鉛を用いたところ、
結合剤合金のクロムが黒鉛の炭素と炭化物を生成し、層
の特性に悪影響を与えることとなった。Highly resistant composite layers are known in which tungsten carbide (WC) functions as a hard material and particles of the hard material are fixed by a matrix of cobalt-chromium alloy. This matrix, ie the binder alloy, has a lubricating effect, but in the case of insufficient lubrication, the effect is insufficient. Therefore, it is necessary to mix the solid lubricant.
One attempt was to use graphite as a lubricant,
The binder alloy chromium formed graphite carbon and carbides, which adversely affected the properties of the layer.

【０００５】[0005]

【発明が解決しようとする課題】本発明は上記問題点を
解決するためになされたものであって、その目的は、リ
ング及びシリンダブッシュにおける摩耗を極力低減し、
潤滑が不十分である場合にできる限り凝着摩耗が生じな
いようにし、疲労に起因する亀裂が生じないようにし、
潤滑が不足する場合に備えて適正な固形潤滑剤を層の中
に貯えておく複合コーティングを提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object thereof is to reduce wear on rings and cylinder bushes as much as possible.
If there is insufficient lubrication, avoid cohesive wear as much as possible and avoid cracks due to fatigue,
The object is to provide a composite coating which stores the proper solid lubricant in the layer in case of lack of lubrication.

【０００６】[0006]

【課題を解決するための手段】上記目的を達成するた
め、本発明のコーティングでは、潤滑剤の各粒子は潤滑
剤の成分と、結合剤合金及び硬質材料の粒子の成分とが
結合することを実質的に阻止する。To achieve the above object, in the coating of the present invention, each particle of the lubricant is formed by combining the component of the lubricant with the component of the particles of the binder alloy and the hard material. Practically prevent.

【０００７】[0007]

【発明の実施の形態】以下、本発明を具体化した一実施
形態を図１〜図３に従って説明する。図１に示す摩滅に
対して耐性を有する耐摩耗性コーティングとしての複合
層１は中間層１０を介して基板２に接合されている。複
合層１は硬質材料の粒子３（極度に大きく図示）と固形
の潤滑剤６を有する粒子５との混合物を備えている。粒
子３及び粒子５は結合剤合金４の中に埋入するように組
み込まれている。各粒子５は潤滑剤６及び保護外被７、
即ちシースを備えている（図２を参照）。中間層１０は
潤滑剤粒子を有さず、複合層１を基板２に効果的に結合
している。また、中間層１０は省略可能である場合が多
い。BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described below with reference to FIGS. The composite layer 1 shown in FIG. 1 as a wear resistant coating resistant to abrasion is bonded to the substrate 2 via an intermediate layer 10. The composite layer 1 comprises a mixture of particles 3 of hard material (illustrated extremely large) and particles 5 with a solid lubricant 6. Particles 3 and 5 are embedded in the binder alloy 4 so as to be embedded therein. Each particle 5 comprises a lubricant 6 and a protective jacket 7,
That is, it has a sheath (see FIG. 2). The intermediate layer 10 has no lubricant particles and effectively bonds the composite layer 1 to the substrate 2. In many cases, the intermediate layer 10 can be omitted.

【０００８】図２の具体例において、潤滑剤６は約１０
〜３０μｍの範囲の長さ及び約５〜１０μｍの範囲の幅
を有する小板形をなす約２５重量％の黒鉛の粒子６によ
り形成されている。保護外被７（いわゆる「シェリット
ゴードン法」により生成）はニッケルからなり、粒子５
全体の約７５％を有している。通常、黒鉛粒子の各保護
外被７は、金属が炭化物を生成しない金属相から形成可
能である。この場合、特にCo，Ni，Cu，及び／又はMoを
金属元素として選択可能である。外被７は間隙７ａを有
することも可能であり、この間隙７ａを介し、溶射法の
実施中に少量の炭素が気相に変換される。In the embodiment of FIG. 2, the lubricant 6 is about 10
It is formed by about 25% by weight of graphite particles 6 in the form of platelets having a length in the range of -30 μm and a width in the range of about 5-10 μm. The protective jacket 7 (produced by the so-called “Sherrit Gordon method”) is made of nickel and contains particles 5
It has about 75% of the total. In general, each protective envelope 7 of graphite particles can be formed from a metal phase in which the metal does not form carbides. In this case, Co, Ni, Cu, and / or Mo can be selected as the metal element. The jacket 7 can also have a gap 7a, through which a small amount of carbon is converted into the vapor phase during the execution of the thermal spraying process.

【０００９】潤滑剤粒子は複合層１に対して均等に分布
していなければならない。黒鉛相は、複合層１が弱体化
しないように、多くて２０体積％を構成するようにす
る。黒鉛相の存在により層面の加工性が向上している。The lubricant particles should be evenly distributed with respect to the composite layer 1. The graphite phase constitutes at most 20% by volume so that the composite layer 1 is not weakened. The presence of the graphite phase improves the workability of the layer surface.

【００１０】２５重量％に達する炭素比を有するニッケ
ル外被を備えた黒鉛粒子の粉末が、ふるい分析−８８＋
４４μｍ（即ち、８８μｍより粗いものが５％、４４μ
ｍより細かいものが２％）により特徴付けられる大きさ
の分布を有する粒子を用いて使用されている。A powder of graphite particles with a nickel jacket having a carbon ratio of up to 25% by weight was found to be Sieve Analysis-88 +.
44μm (ie 5% coarser than 88μm, 44μ
More than m is used with particles having a size distribution characterized by 2%).

【００１１】図３は図２と同一の拡大率で表され、硬質
材料の粒子３ａ（WC）及び結合剤合金３ｂ（１０重量％
のCo、４重量％のCr）からなる平面研削された（研削面
３０）粉末粒子３を示す。結合剤合金３ｂはCo及びCrか
らなるマトリックスを形成し、Coの重量比はCrの重量比
より大きく２．５の比率である。このマトリックスは細
孔密度が比較的低く、本質的に耐摩耗性が高い。上記の
組成の代替として別の組成も選択可能である。例えば、
マトリックスはCo，CoCr，Mo又はこれら材料の混合物か
らなることも可能である。結合剤合金３ｂは炭化物生成
成分を有することが可能である。硬質材料相は金属元素
W，Cr，Ti，Ta，Mo，Nb，Zr，Hf及びVの炭化物、窒化物
又は窒化炭素により形成可能である。FIG. 3 is represented by the same enlargement ratio as FIG. 2, in which the particles 3a (WC) of the hard material and the binder alloy 3b (10% by weight) are used.
Of Co, 4% by weight of Cr) is shown, and the surface-ground (ground surface 30) powder particles 3 are shown. The binder alloy 3b forms a matrix composed of Co and Cr, and the weight ratio of Co is larger than that of Cr and is 2.5. This matrix has a relatively low pore density and is inherently highly wear resistant. As an alternative to the above composition, another composition can be selected. For example,
The matrix can also consist of Co, CoCr, Mo or a mixture of these materials. The binder alloy 3b can have a carbide forming component. Hard material phase is metallic element
It can be formed of W, Cr, Ti, Ta, Mo, Nb, Zr, Hf and V carbides, nitrides or carbon nitrides.

【００１２】硬質材料相及び結合剤合金３ｂを有する粉
末粒子３は、成分の焼結、そして焼結生成物の粉砕によ
り生成可能である。使用粉末の粒子の大きさはふるい分
析−４５＋１１μｍにより特徴付けられる。Powder particles 3 having a hard material phase and a binder alloy 3b can be produced by sintering the components and grinding the sintered product. The particle size of the powder used is characterized by sieving analysis −45 + 11 μm.

【００１３】従来のコーティングの問題点を解決するよ
うに、本発明では保護外被７、即ちシースにより被われ
た個々の潤滑剤粒子を用いている。通常、この種の保護
外被７により潤滑剤６の成分と、結合剤合金４及び硬質
材料の成分とが結合することを阻止している。保護外被
が完全には無傷ではない時であっても、上記のような複
合物の生成は実質的に阻止される。In order to overcome the problems of conventional coatings, the present invention uses individual lubricant particles covered by a protective jacket 7, or sheath. Normally, this type of protective jacket 7 prevents the components of the lubricant 6 from binding to the components of the binder alloy 4 and the hard material. Even when the protective jacket is not completely intact, the formation of such composites is substantially prevented.

【００１４】本発明の保護層を有する機械部品には、例
えばピストンリングや、ターボ機械（即ち、タービン、
ポンプ等）のベアリング及びシールがある。本発明では
保護層を施すには溶射法を用いている。Machine parts having a protective layer of the present invention include, for example, piston rings, turbomachines (ie turbines,
Bearings and seals for pumps). In the present invention, the thermal spraying method is used to apply the protective layer.

【００１５】最適なコーティングを施すことを可能にす
るには、複数のサブテストを備えたテストプログラムを
実行せねばならない。これらテストにおいて、広範囲に
及ぶ複数のパラメータを変化させる必要がある。溶射法
において、これら複数のパラメータには以下のパラメー
タがある。第１は噴霧用粉末の組成であり、これは硬質
材料／結合剤合金３ｂの粒子と、潤滑剤粒子との混合物
である。第２は酸素−燃料ガスの比率である。第３は粉
末供給率である。第４はスプレーノズルと基板との間の
相対速度である。第５はノズルと基板との距離である。In order to be able to apply the optimum coating, a test program with several subtests must be run. In these tests, it is necessary to change a wide range of parameters. In the thermal spraying method, the plurality of parameters include the following parameters. The first is the composition of the atomizing powder, which is a mixture of particles of hard material / binder alloy 3b and lubricant particles. The second is the oxygen-fuel gas ratio. Third is the powder supply rate. The fourth is the relative velocity between the spray nozzle and the substrate. The fifth is the distance between the nozzle and the substrate.

【００１６】コーティング中に有効に組み込まれた噴霧
用粉末の比率が測定される。勿論、極力喪失しないよう
にする。得られた試料は以下の特性について検査され
る。第１は硬質材料、結合剤合金４及び潤滑剤６の相の
間における関係、即ち比率である。第２は層面の粗さで
ある。第３は硬度である（０．３ｋｇの荷重下における
ダイアモンドチップの貫入深度の測定単位であるビッカ
ースピラミッド硬度ＨＶ 0.3）。第４は多孔度である。Spray effectively incorporated into the coating
The ratio of powder for use is measured. Of course not to lose as much as possible
To The obtained samples were inspected for the following properties:
It The first is of the phases of hard material, binder alloy 4 and lubricant 6.
It is the relationship, or ratio, between. The second is the roughness of the layer surface.
is there. The third is hardness (under a load of 0.3 kg)
Vickers, a unit of measurement of the penetration depth of diamond chips
Spyramid hardness HV 0.3). The fourth is porosity.

【００１７】耐摩耗性を判定すべく、摩滅テストが行わ
れる。これらテストでは、所定の荷重により回転プレー
トに対してピンが押圧される。従って、テストされるコ
ーティングはピンの接触面を形成し、その摩耗率が測定
される。これらテストにおいて、「すり減り痕」の兆候
に対する臨界荷重が判定される。A wear test is performed to determine the wear resistance. In these tests, the pin is pressed against the rotating plate by a predetermined load. Therefore, the coating tested forms the contact surface of the pin and its wear rate is measured. In these tests, the critical load for the sign of "scratch scars" is determined.

【００１８】HVOF（高速酸素燃料、High Velocity Oxy-
Fuel）法、即ち、高速にて酸素及び燃料ガスの混合物を
燃焼することにより噴霧用粉末が基板上に施される溶射
法により、好適な結果が得られる。燃料ガスとしてプロ
パンが使用され、プロパンに対する酸素比が約５〜１０
の間の範囲の値に選択される。１００ｍｍサイズのノズ
ルが用いられる（ズルツァーメトコ社(Sulzer Metco)の
CDC(連続デトネーション噴霧、Continuous Detonation
Spraying)標準１００mmノズル）。HVOF (High Velocity Oxy-
The Fuel method, i.e., the thermal spraying method, in which the atomizing powder is applied to the substrate by burning a mixture of oxygen and fuel gas at high speed, gives good results. Propane is used as the fuel gas and has an oxygen to propane ratio of about 5-10.
Selected to a value in the range between. A 100 mm size nozzle is used (from Sulzer Metco)
CDC (Continuous Detonation Spray)
Spraying) Standard 100mm nozzle).

【００１９】テストを実施する際、粉末混合物には以下
の組成物が選択される。即ち、８４重量％のWC、１０重
量％のCo、４重量％のCr（この場合、WC、Co及びCrの比
率はそれぞれ約８６重量％，１０重量％及び４重量％に
達する）、及び１０〜２０重量％、詳細には１６重量％
の２５重量％に達する炭素比を有するニッケル外被を備
えた黒鉛粒子である。In carrying out the test, the following compositions are selected for the powder mixture: That is, 84 wt% WC, 10 wt% Co, 4 wt% Cr (in this case, the proportions of WC, Co and Cr reach about 86 wt%, 10 wt% and 4 wt% respectively), and 10 ~ 20% by weight, specifically 16% by weight
Graphite particles with a nickel jacket having a carbon ratio of up to 25% by weight.

【００２０】特定の統計法（「部分要因分析法(fractio
nal factorial experimental design)」、例えば、１９
７８年、ジェー．ワイリーアンドサンズ社(J. Wiley &
Sons)発行の「実験者のための統計学−配置、データ分
析及びモデル構成(Statisticsfor Experimenters - An
Introduction to Design, Data and Model Buildin
g)」，ダブリュ．ジー．ハンター(W.G. Hunter)、ジェ
ー．エス．ハンター(J.S. Hunter)(著)を参照された
い。）を用いて、８回のみの連続テストによりほぼ最適
なコーティングが期待されるパラメータ値を見出すこと
が可能である。以下の値はこの方法を用いて得られたも
のである。酸素と燃料ガスとの比率は７．０であり、粉
末供給率は分速３５ｇであり、噴射ノズルと基板との相
対速度は分速７２ｍであり、ノズルと基板との距離は２
５０ｍｍである。A specific statistical method (“partial factor analysis method (fractio
nal factorial experimental design) ”, for example, 19
1978, J. Wiley & Sons (J. Wiley &
Sons) `` Statistics for Experimenters-An
Introduction to Design, Data and Model Buildin
g) ”, W. Gee. Hunter (WG Hunter), J. S. See JS Hunter (Author). ), It is possible to find parameter values for which a near-optimal coating is expected with only 8 consecutive tests. The following values were obtained using this method. The ratio of oxygen to fuel gas was 7.0, the powder supply rate was 35 g / min, the relative speed between the injection nozzle and the substrate was 72 m / min, and the distance between the nozzle and the substrate was 2 m.
50 mm.

【００２１】パラメータの選択は以下の値に関連してい
る。噴霧用粉末の喪失は２６％であり（即ち、施工率は
７４％である。）、ビッカースピラミッド硬度ＨＶ0.3
は８５９であり、黒鉛相の比率は８体積％であり（Ｘ線
測定をもとに推計された値）、WC及びW2C（一炭化二タ
ングステン）の比率は５．２である（黒鉛の場合と同様
の推定値）。ピン及び回転ディスクを用いた摩滅テスト
は室温にて８８Ｎ／ｍｍ2 で凝着摩耗（「すり減り
痕」）の兆候を示した。２２０℃における該値は５９Ｎ
／ｍｍ2に達する。これら値は１００重量％のWC、１０
重量％のCo、４重量％のCrを有し、即ち潤滑成分が存在
しない場合におけるコーティングの値より約２０％優れ
ている。溶射法の実施中にWCの一部はW2Cに変換され
る。この変換は硬質材料相の耐摩耗性に対して負の作用
をなす。なお、噴霧中に黒鉛の一部が気相に変化するこ
とが示された。気化炭素はWCの変換を軽減する効果を奏
し、好ましくないW2Cの生成が阻止される。The choice of parameters is associated with the following values: The loss of spraying powder is 26% (that is, the construction rate is 74%) and the Vickers Pyramid hardness HV 0.3.
Is 859, the ratio of the graphite phase is 8% by volume (value estimated based on X-ray measurement), and the ratio of WC and W 2 C (di-tungsten monocarbide) is 5.2 (graphite. Similar estimates as in. Abrasion tests using pins and rotating disks showed signs of adhesive wear ("scratch marks") at room temperature at 88 N / mm 2 . The value at 220 ℃ is 59N
/ Mm 2 is reached. These values are 100% by weight WC, 10
It has wt% Co, 4 wt% Cr, ie about 20% better than the value of the coating in the absence of a lubricating component. Part of WC is converted to W 2 C during the spraying process. This conversion has a negative effect on the wear resistance of the hard material phase. In addition, it was shown that a part of graphite changed into a gas phase during spraying. Vaporized carbon has the effect of reducing the conversion of WC and prevents the undesirable formation of W 2 C.

【００２２】[0022]

【発明の効果】以上詳述したように、本発明によれば、
リング及びシリンダブッシュにおける摩耗を極力低減
し、潤滑が不十分である場合にできる限り凝着摩耗が生
じないようにし、疲労に起因する亀裂が生じないように
し、潤滑が不足する場合に備えて適正な固形潤滑剤を層
の中に貯えておくことができるという優れた効果があ
る。As described in detail above, according to the present invention,
Minimize wear on rings and cylinder bushes to prevent adhesive wear as much as possible when lubrication is inadequate, to prevent cracks caused by fatigue, and to be prepared in case of insufficient lubrication. There is an excellent effect that various solid lubricants can be stored in the layer.

【図面の簡単な説明】[Brief description of drawings]

【図１】 本発明によるコーティングを示す断面図。1 is a cross-sectional view showing a coating according to the present invention.

【図２】 ２５重量％に達する炭素比を有するニッケル
外被を備えた黒鉛粒子を示す一部破断側面図。FIG. 2 is a partially cutaway side view showing a graphite particle with a nickel jacket having a carbon ratio of up to 25% by weight.

【図３】 WC、１０重量％のCo、４重量％のCr粒子を示
す一部破断側面図。FIG. 3 is a partially cutaway side view showing WC, 10 wt% Co, and 4 wt% Cr particles.

【符号の説明】[Explanation of symbols]

１…耐摩耗性コーティングとしての複合層、２…基板、
３，５…粒子、３ｂ，４…結合剤合金、６…潤滑剤、７
…保護外被。1 ... Composite layer as abrasion resistant coating, 2 ... Substrate,
3, 5 ... Particles, 3b, 4 ... Binder alloy, 6 ... Lubricant, 7
… Protective jacket.

Claims (13)

【特許請求の範囲】[Claims] 【請求項１】 基板（２）上に配置されるとともに、硬
質材料の粒子（３）及び固形の潤滑剤（６）の粒子
（５）の混合物を有する耐摩滅性を有する複合コーティ
ングにおいて、 前記潤滑剤（６）の各粒子（５）は潤滑剤（６）の成分
と、結合剤合金（４）及び硬質材料の粒子（３）の成分
とが結合することを実質的に阻止することを特徴とする
コーティング。1. A wear-resistant composite coating, which is arranged on a substrate (2) and comprises a mixture of particles (3) of hard material and particles (5) of solid lubricant (6), Each particle (5) of the lubricant (6) substantially prevents binding of the components of the lubricant (6) with the components of the binder alloy (4) and the particles of hard material (3). Characteristic coating. 【請求項２】 前記固形の潤滑剤（６）は黒鉛であり、
結合剤合金（４）及び硬質材料の粒子（３）のうち少な
くともいずれかは炭化物生成成分を有し、黒鉛粒子の各
保護外被（７）は金属相から生成され、該金属相の金属
元素は炭化物を生成せず、該金属元素は詳細にはCo（コ
バルト）、Ni（ニッケル）、Cu（銅）及びMo（モリブデ
ン）のうちの少なくともいずれか１つであることを特徴
とする請求項１に記載のコーティング。2. The solid lubricant (6) is graphite,
At least one of the binder alloy (4) and the hard material particle (3) has a carbide-forming component, and each protective jacket (7) of the graphite particle is generated from a metal phase, and the metal element of the metal phase. Does not form a carbide, and the metal element is at least one of Co (cobalt), Ni (nickel), Cu (copper), and Mo (molybdenum). 1. The coating according to 1. 【請求項３】 前記結合剤合金（４）は細孔密度が低い
とともに本質的に耐摩耗性が高い相を形成し、かつ詳細
にはCo，CoCr（コバルトクロム）、Mo及びこれら材料の
混合物のいずれか１つからなることを特徴とする請求項
１に記載のコーティング。3. The binder alloy (4) forms a phase with low pore density and essentially high wear resistance, and in particular Co, CoCr (cobalt chromium), Mo and mixtures of these materials. The coating according to claim 1, wherein the coating comprises any one of: 【請求項４】 前記結合剤合金（４）はCo及びCr（クロ
ム）からなり、Coの重量比はCrの重量比の約２〜３倍の
大きさであることを特徴とする請求項３に記載のコーテ
ィング。4. The binder alloy (4) is composed of Co and Cr (chromium), and the weight ratio of Co is about 2 to 3 times the weight ratio of Cr. The coating described in. 【請求項５】 前記硬質材料の粒子（３）は金属元素で
あるW（タングステン）、Cr、Ti（チタン）、Nb（ニオ
ブ）、Zr（ジルコニウム）、Hf（ハフニウム）、Ta（タ
ンタル）及びMoのうちの少なくともいずれか１つの炭化
物、窒化物及び窒化炭素の少なくともいずれか１つを有
することを特徴とする請求項１乃至請求項４のいずれか
１項に記載のコーティング。5. The particles (3) of the hard material are metallic elements W (tungsten), Cr, Ti (titanium), Nb (niobium), Zr (zirconium), Hf (hafnium), Ta (tantalum) and The coating according to any one of claims 1 to 4, comprising at least one of carbide, nitride and carbon nitride of at least one of Mo. 【請求項６】 機械部品の表面の少なくとも一部が耐摩
耗性状にコーティングされることを特徴とする請求項１
乃至請求項５のいずれか１項に記載の耐摩耗性コーティ
ングを有する機械部品。6. A machine part having at least a part of its surface coated with wear resistance.
A machine part having the wear resistant coating according to claim 5. 【請求項７】 前記潤滑剤（６）の粒子（５）を有さな
い複合層（１０）は基板（２）を形成する基体と耐摩耗
性コーティング（１）との間に配置されることを特徴と
する請求項６に記載の部品。7. A composite layer (10) free of particles (5) of the lubricant (6) is arranged between the substrate forming the substrate (2) and the abrasion resistant coating (1). A component according to claim 6, characterized in that 【請求項８】 外被（７）に被われた潤滑剤（６）の粒
子（５）と、硬質材料の粒子（３ａ）及び結合剤合金
（３ｂ）の双方を含有する粒子（３）とを有する噴霧用
粉末には、混合物が使用されることを特徴とする請求項
１乃至請求項５のいずれか１項に記載の基板上のコーテ
ィングをするための溶射法。8. Particles (5) of a lubricant (6) covered by a jacket (7) and particles (3) containing both particles (3a) of hard material and a binder alloy (3b). A spraying method for coating on a substrate according to any one of claims 1 to 5, characterized in that a mixture is used for the spraying powder with. 【請求項９】 前記粉末混合物は高速にて酸素及び燃料
ガスの混合物を燃焼することにより、即ちHVOF法により
基板に施されることを特徴とする請求項８に記載の方
法。9. Method according to claim 8, characterized in that the powder mixture is applied to the substrate by burning a mixture of oxygen and fuel gas at high speed, ie by the HVOF method. 【請求項１０】 前記潤滑剤（６）は黒鉛であり、潤滑
剤（６）の粒子（５）はNi外被を有するとともに約２５
重量％の黒鉛を有して小板形であり、各小板は約１０〜
３０μｍの範囲の長さ及び約５〜１０μｍの範囲の幅を
有することを特徴とする請求項８及び請求項９のいずれ
か１項に記載の方法。10. The lubricant (6) is graphite and the particles (5) of the lubricant (6) have a Ni jacket and about 25.
It has a platelet shape with weight% graphite and each platelet is about 10
10. A method according to any one of claims 8 and 9 having a length in the range of 30 [mu] m and a width in the range of about 5-10 [mu] m. 【請求項１１】 前記燃料ガスとしてプロパンが使用さ
れ、プロパンに対する酸素比が約５〜１０の間の範囲の
値に選択されることを特徴とする請求項９及び請求項１
０に記載の方法。11. Propane is used as the fuel gas and the oxygen to propane ratio is selected to a value in the range between about 5 and 10.
The method described in 0. 【請求項１２】 前記硬質材料相及び結合剤合金相を有
する粉末粒子は、成分の焼結、そして焼結生成物の粉砕
により生成され、WC（炭化タングステン）、Co及びCrの
比率がそれぞれ約８６重量％，１０重量％及び４重量％
に達することを特徴とする請求項８乃至請求項１１のい
ずれか１項に記載の方法。12. The powder particles having the hard material phase and the binder alloy phase are produced by sintering the components and pulverizing the sintered product, and the ratio of WC (tungsten carbide), Co and Cr is about each. 86% by weight, 10% by weight and 4% by weight
12. A method according to any one of claims 8 to 11, characterized in that 【請求項１３】 前記粉末混合物には１０〜２０重量
％、詳細には約１６重量％のニッケル−黒鉛粉末が選択
されることを特徴とする請求項１０又は請求項１２に記
載の方法。13. A method according to claim 10 or 12, characterized in that 10 to 20% by weight, in particular about 16% by weight, of nickel-graphite powder is selected for the powder mixture.
JP7333729A 1995-02-02 1995-12-21 Composite coating having abrasion resistance Pending JPH08253877A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE95810072-9 1995-02-02
EP95810072A EP0725158B1 (en) 1995-02-02 1995-02-02 Wear- and slip resistant composite coating

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Publication Number Publication Date
JPH08253877A true JPH08253877A (en) 1996-10-01

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EP (1) EP0725158B1 (en)
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DE (1) DE59506236D1 (en)

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EP0725158B1 (en) 1999-06-16

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